Cross-metathesis reaction of vinyl sulfones and sulfoxides

Article abstract of DOI:10.1016/S0040-4020(03)00682-3

Cross-metathesis reactions of α,β-unsaturated sulfones and sulfoxides in the presence of molybdenum and ruthenium pre-catalysts were tested. A selective metahesis reaction was achieved between functionalized terminal olefins and vinyl sulfones by using th

Full text of DOI:10.1016/S0040-4020(03)00682-3

Tetrahedron 59 (2003) 4525–4531
Cross-metathesis reaction of vinyl sulfones and sulfoxides
*
Anna Michrowska, Michał Bieniek, Mikhail Kim, Rafał Klajn and Karol Grela
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 4452, P.O.B. 58, PL01-224 Warsaw, Poland
Received 27 January 2003; revised 31 March 2003; accepted 29 April 2003
Abstract—Cross-metathesis reactions of a,b-unsaturated sulfones and sulfoxides in the presence of molybdenum and ruthenium pre-
catalysts were tested. A selective metahesis reaction was achieved between functionalized terminal olefins and vinyl sulfones by using the
‘second generation’ ruthenium catalysts 1c–h while the highly active Schrock catalyst 1b was found to be functional group incompatible
with vinyl sulfones. The cross-metathesis products were isolated in good yields with an excellent (E)-selectivity. Both the molybdenum and
ruthenium-based complexes were, however, incompatible with a,b- and b,g-unsaturated sulfoxides. q 2003 Published by Elsevier Science
Ltd.
1. Introduction
disulfides, and dithianes and even in the self-cross
metathesis reaction of thiols.6b
Sulphur chemistry has been a standard part of synthetic
organic chemistry for more than one century. A variety of
versatile sulfur-containing synthons is known today, and
among those, a,b-unsaturated sulfones have attracted
special attention as they can be transformed into versatile
synthetic intermediates. These compounds serve efficiently
as, e.g. Michael acceptors and as 2p partners in cyclo-
addition reactions. In addition, the easy further transform-
ations of sulfur group via elimination or either reductive or
alkylative desulfonylation render further advantages of
these compounds in synthesis.1
The compatibility of remote sulfone function with
ruthenium and molybdenum-based metathesis catalysts is
well established.8 The cross-metathesis of allyl sulfone has
been reported by Grubbs.9 Recently, Yao has published a
very elegant method for the preparation of cyclic sulfones
by RCM or enyne metathesis of various diallyl and
homoallyl sulfones.10 Also preparation of unsaturated
sultams and sultones from a,w-unsaturated sulfonamides11
and sulfonates12 has been described (Scheme 1).
Although, after publication of our preliminary communi-
cation,2 some examples of metathesis of conjugated
sulfones have been reported,13 applications of such
substrates in metathesis remain rare. Similarly, according
to our best knowledge the cross metathesis reaction of vinyl
sulfoxides has not yet been reported.
In our preliminary communication2 we have described a
simple (E)-selective method of preparation of substituted
unsaturated sulfones based on olefin cross-metathesis (CM)
of phenyl vinyl sulfone catalyzed by the ‘second generation’
Grubbs’ carbene3 1c.
Several sulfur-containing alkenes have been applied as
substrates in metathesis reactions. The ‘first generation’
ruthenium pre-catalysts,4 such as 1a are known to be of low
or no reactivity toward the RCM of a,w-dienes containing
sulfide and disulfide moieties, whereas Schrock moly-
bdenum complex5 1b was found to be more compatible with
these substrates.6a More recently, a study has been
published to show that the ‘second generation’ Nolan-type
pre-catalyst7 1e acts in such transformation extremely well,
and can be successfully employed in metathesis of sulfides,
In order to fill these empty places in the electron deficient
alkenes-metathesis catalysts ‘compatibility matrix’ we
decided to screen the catalytic activity of selected
molybdenum and ruthenium carbenes 1a–h with represen-
tative a,b-unsaturated sulfur-contained compounds.
2. Results and discussion
We used the previously optimised2 cross-metathesis of
olefin 2a and phenyl vinyl sulfone 3a as a model
transformation (Table 1) in this investigation. The ‘first-
generation’ Grubbs’ alkylidene4 1a did not promote cross-
metathesis with a,b-unsaturated sulfone and under these
conditions only the product of alkene self-metathesis 5a was
observed (entry a). More interestingly, the very reactive
Keywords: carbene complex; olefin metathesis; sulfone; ruthenium;
homogenous catalysis.
*
Corresponding author. Tel.: þ48-22-632-32-21; fax: þ48-22-632-66-81;
e-mail: grela@icho.edu.pl
0040–4020/03/$ - see front matter q 2003 Published by Elsevier Science Ltd.
doi:10.1016/S0040-4020(03)00682-3

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A. Michrowska et al. / Tetrahedron 59 (2003) 4525–4531
Scheme 1. The catalysts for olefin metathesis.
Schrock molybdenum catalyst5 1b was the most probably
completely poisoned by 3a, as neither product 4a nor
‘homodimer’ 5a were formed after 15 h of the reaction
(entry b). Although molybdenum alkylidene 1b effects
CM reactions of some a,b-unsaturated substrates
(e.g. acrylonitrile),14 our observation suggest that vinyl
sulfones constitute a class of substrates which are not
functional group compatible with this very sensitive
catalyst.
The commercially available divinyl sulfone 3b can be also
used in the CM with terminal alkenes. In this case we
considered that metathesis can occur at one or both CvC
bonds of 3b. Fortunately, when divinyl sulfone 3b was used
in excess (3b/olefin 2:1 molar ratio), the very clean and
selective formation of only ‘monosubstituted’ products (E)-
4j–l was observed. Attempts to prepare divinyl sulfone
functionalized at both sides, such as the compound 6k, were
less rewarding, and even under forcing conditions (2k/3b
4:1) the monosubstituted 4k was the predominant sulfone-
product formed (Fig. 1).
All ‘second-generation’ NHC-ruthenium complexes, in
contrast, effect the formation of corresponding product 4a
(entries c–g).15 With these pre-catalysts we also observed
the formation of small amounts of ‘homodimer’ 5a which
decreased significantly after prolongated stirring. As it can
be seen from Table 1, all NHC-containing complexes gave
similarly high yields ($80%), although in respect to the
reaction selectivity (cross- versus homometathesis) and
over-all conversion the Nolan-type pre-catalyst7 1e and the
phosphine-free carbene16 1h were found to be superior to
the other catalysts tested (entries d and g). In line with the
previous observation2 the CM of 1a and phenyl vinyl
sulfone was in all cases highly stereoselective, as the (E)-4a
was the only isomer detected by GC and NMR.
Unfortunately, geminal disubstituted olefins (2m–o) failed
to react with 3a even when the most active ruthenium
complex 1e was used. Similarly, a-substituted-a,b-unsatu-
rated sulfones (3c–d) were unreactive in the model
reaction with 2a, suggesting that the cross-metathesis of
a,b-unsaturated sulfones is very sensitive to steric
hindrance (Fig. 2).
We next examined the cross-metathesis of vinyl sulfoxides.
To our surprise the commercially available phenyl vinyl
sulfoxide 3e failed to react with model alkene 2a, and the
starting materials were recovered after the reaction almost
quantitatively. Both the molybdenum (1b) and ruthenium-
based catalysts (1c) were tested and neither product 7a nor
‘homodimer’ 5a were observed (Scheme 2). One example of
application of sulfoxide in metathesis has recently been
Having identified ruthenium complexes 1c–g as effective
catalysts for this transformation, we decided to extend this
investigation to a more diverse set of substituted and
sterically demanded substrates. The results compiled in
Table 2 illustrate the scope and synthetic utility of sulfone
cross-metathesis. Thus substrates bearing various function-
ality, including O–H (entries b, c, g) and C–H acids (entry
f) can be easily converted to corresponding a,b-unsaturated
sulfones in good yields. In all reported cases the (E)-isomer
was the only sulfone product detected by GC or NMR.
Dimerisation products 5a–d,f of the terminal olefin were
observed only in minute amounts. It is well established that
Hoveyda-type catalysts display higher reactivity towards a
broad range of electron-deficient substrates.13b,16,17 Indeed,
the highly active carbene 1h, recently introduced by our
group,16 proved to be the catalyst of choice for this
transformation.
Table 1. Cross-metathesis between olefins 2a–l (1 equiv.) and sulfones
2a,b (2 equiv.)
Entry
Catalyst
GC Yield (%)a
a
b
c
d
e
1a
1b
1c
1e
1f
0
82 (85)
0
0
92 (.99)
98 (.99)
87 (91)
80 (89)
95 (.99)
8 (,1)
2 (,1)
13 (9)
16 (11)
5 (,1)
More sterically crowded substrates such as 2h–i gave
somewhat lower yields. It has been claimed that ruthenium
carbene complex 1c, bearing a ‘saturated’ NHC ligand,
shows higher reactivity then its ’unsaturated’ congener, 1e.3
In the light of these observations we were surprised to find
that in this particular case 1c was clearly inferior not only to
1h but also to Nolan catalyst 1e.
f
gb
1g
1h
a
GC yield after 3 h of reaction. In parentheses are the GC yields after 15 h
of reaction.
GC yield after 1 h of reaction.
b

A. Michrowska et al. / Tetrahedron 59 (2003) 4525–4531
4527
Table 2. Screening of the catalysts 1a–h
Entry
a
Olefin 2a–l
Sulphone 3a,b
Product 4a–l
Cat. 1
Yield (%)a
2a
4a
1c
1h
85
90b
b
3a
1c
(81)c
96
c
3a
3a
3a
1h
dd
ee
1c
1h
68
86
1c
1h
26
33
f
3a
3a
3a
1c
1g
74
g
h
71
1c
1e
1g
1h
(55)c
53
30
48
1c
1e
1g
1h
(33)c
44 (54)c
41
i
3a
53
j
1c
1c
1c
59
42
84
k
3b
3b
l
2d
a
Isolated yields of analytically pure compounds. All reactions were carried out with 5 mol% of 1c–h in refluxing CH2Cl2 for 3–24 h, unless stated otherwise.
Reaction with 2.5 mol% of 1h, 258C.
Reaction with 10 mol% of 1c–e, reflux.
Reaction with 5 mol% of 1c or 1h, 258C. Yield determined by GC.
Reaction of 3 equiv. of olefin 2e with 1 equiv. of sulphone 3a.
b
c
d
e
Figure 1.
Figure 2.

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A. Michrowska et al. / Tetrahedron 59 (2003) 4525–4531
Scheme 2. Cross metathesis of vinyl and allyl sulfoxides. (a) Reaction of 2b (1 equiv.) with vinyl sulfone 3a or sulfoxide 3e (2 equiv.) and allyl sulfone 8a
or sulfoxide 8b (2 equiv.) in refluxing CH2Cl2, 15 h. Yields based on GC. (b) With 10 mol% of 1c. (c) DMSO (50 equiv. relative to 1c) was added.
(d) (E)/(Z)¼84:16 (GC). Isolated yield.
described.18 The RCM reaction of a substituted vinyl
sulfoxide and 1a was the key step cyclisation in route to
(^)-securinine, a member of the Securinega family of
alkaloids. It is notable that this transformation was achieved
by the stoichiometric amount of the complex 1a, while the
use of 1a in catalytic amounts was ineffective.18 To the best
of our knowledge, except this single example, the meta-
thesis of unsaturated sulfoxides has not been reported in the
literature.19 Therefore, we decided to study in more detail
the behaviour of sulfoxide function in olefin metathesis. To
do so, we compared CM reactions of a b,g-unsaturated
sulfones9 and sulfoxides. We have found that in contrast to
allyl sulfone 8a, allyl sulfoxide 8b has failed to react with
the model alkene 2a (Scheme 2). Georg has recently
demonstrated the ability of dimethylsulfoxide (DMSO) to
sequester traces of ruthenium.20 In our control experiment
DMSO (50 equiv. relative to 1c) almost completely
inhibited the cross-metathesis between olefin 2a and sulfone
3a (Scheme 2). Therefore, we suppose that the observed
lack of reactivity with sulfoxide bearing alkenes is due to
the poisoning of catalyst by ligation of metal by a sulfoxide
function.21
phenone), toluene (Na), n-pentane, n-hexane, CH2Cl2
(CaH2), Et2O (LiAlH4). Flash column chromatography:
Merck silica gel 60 (230–400 mesh). NMR: Spectra were
recorded on Bruker AVANCE 500, Varian Gemini 200 and
400 spectrometers in CDCl3; chemical shifts (d) are given in
ppm relative to TMS, coupling constants (J) in Hz. IR:
Perkin–Elmer Spectrum 2000 FT-IR. MS (EI, LSIMS):
AMD 604 Intectra GmbH. MS (ESI): Mariner Perseptive
Biosystems, Inc. Micro-analyses were provided by Institute
of Organic Chemistry, PAS, Warsaw. All commercially
available substrates were used as received. All other
chemicals or reagents were prepared according to literature
procedures: 2g–h,22a 2i,22b 2n–o,22c 3c,22d 3d.22e
4.2. Hoveyda-type carbene (1g)
4.2.1. 2-Isopropoxy-5-bromostyrene. To a suspension of
NaH (60% in oil, 687 mg, 17.2 mmol) in DMF (15 mL) a
solution of 2-hydroxy-5-bromobenzaldehyde (2.527 g,
12.5 mmol) in DMF (15 mL) was added dropwise at rt.
After 30 min of stirring 2-iodopropane (2 mL, 19.0 mmol)
was added. After stirring at rt for 24 h, DMF was removed
under vacuum and the residue was poured into water
(50 mL) and extracted with t-BuOMe (4£25 mL). The
combined organic extracts were washed with brine, dried
(Mg2SO4) and concentrated in vacuo. The crude product
(3.0 g) was used directly in the next step.
3. Conclusion
In conclusion, we have demonstrated that vinyl sulfones
readily participate in the CM reaction with terminal
olefins, leading to synthetically useful b-functionalized
a,b-unsaturated sulfones with an excellent (E)-selectivity
under mild conditions. The robust, ‘second generation’
ruthenium complexes 1c–h gave the highest yields, while
the highly active Schrock catalyst 1b was found to be
functional group incompatible with vinyl sulfones. Both the
molybdenum and ruthenium-based complexes were, how-
ever, incompatible with a,b- and b,g-unsaturated
sulfoxides.
To a stirred suspension of Ph3PvCH2 (6.8 g, 16.25 mmol,
2.4 mmol/g) in THF (50 mL) a solution of crude 2-iso-
propoxy-5-bromobenzaldehyde (3.0 g) in THF (10 mL) was
added at 2788C. The reaction mixture was allowed to warm
to rt and was stirred at rt for 1 h before diluted with
t-BuOMe (100 mL). The insoluble material was filtered off
and the crude product was passed through a short column of
silica, concentrated to dryness and distilled in vacuo to give
5 (2.03 g, 67% over two steps) as a colourless oil. Bp 708C/
0.2 Torr. [Found: C, 54.82; H, 5.41. C11H13BrO requires C,
54.79; H, 5.43%] n(film) 3087, 1624, 1479, 1244,
1125 cm21; dH (200 MHz, CDCl3) 1.34 (6H, d, J¼6.0 Hz,
CH(CH3)2), 4.49 (1H, sept, J¼6.0 Hz, CH(CH3)2), 5.27
(1H, dd, J¼1.3, 11.3 Hz, vCH), 5.71 (1H, dd, J¼1.3,
17.8 Hz, CHv), 6.75 (1H, d, J¼8.8 Hz, CHv), 6.98
(1H, dd, J¼17.8, 11.3 Hz, ArH), 7.28 (1H, dd, J¼2.5,
8.8 Hz, ArH), 7.57 (1H, d, J¼2.5 Hz, ArH); dC
(50 MHz, CDCl3) 22.0, 71.26, 113.0, 115.2, 115.9, 129.2,
130.0, 130.8, 131.1, 154.2; m/z (EI) 242 (30, Mþ), 200 (67),
4. Experimental
4.1. General
Unless otherwise noted, all reactions were carried out under
Ar in pre-dried glassware using Schlenk techniques. The
solvents were dried by distillation over the following drying
agents and were transferred under argon: THF (K/benzo-

A. Michrowska et al. / Tetrahedron 59 (2003) 4525–4531
4529
172 (3), 118 (14), 102 (3), 91 (61), 89 (13), 65 (11), 63 (10),
43 (13).
62.86, 127.54, 127.66, 129.23, 130.34, 130.63, 133.24,
140.63, 146.68; m/z (EI) 169 (22), 143 (42), 125 (76), 98
(75), 80 (100), 79 (40), 78 (35), 77 (64), 53 (24), 51 (35), 41
(35); HRMS (LSIMS): MHþ, found 241.0913. C12H17O3S
requires 241.0898.
4.2.2. Hoveyda-type carbene (1g). Carbene complex 1c
(90 mg, 0.106 mmol), CuCl (14 mg, 0.138 mmol) and
CH2Cl2 (5 mL) were placed in a Schlenk flask equipped
with a condenser. A solution of 2-isopropoxy-5-bromo-
styrene (30 mg, 0.127 mmol) in CH2Cl2 (2 mL) was then
added at rt and the resulted solution was stirred at 458C for
1 h. From this point forth, all manipulations were carried out
in air with reagent-grade solvents. The reaction mixture was
concentrated in vacuo and the resulted material was purified
by column chromatography on silica. Elution with 1:1
c-hexane/CH2Cl2 removed a green band from the column.
Removal of solvent, washing with a minimal amount of cold
n-pentane and drying under vacuum afforded 1g (77 mg,
93%) as a bright green microcrystalline solid. dH (500 MHz,
CDCl3) 1.25 (6H, d, J¼6.1 Hz, CH(CH3)2), 2.41 (6H, s,
C6H2(CH3)), 2.47 (12H, s, C6H2(CH3)2), 4.17 (4H, s,
CH2CH2), 4.84 (1H, sept, J¼6.1 Hz, CH(CH3)2), 6.67 (1H,
d, J¼8.7 Hz, ArH), 6.67 (1H, d, J¼8.7 Hz, ArH), 7.04 (1H,
d, J¼2.4 Hz, ArH), 7.08 (4H, s, C6H2(CH3)3), 7.59 (1H, dd,
J¼2.4, 8.7 Hz, ArH), 16.35 (1H, br. s, RuvCH); dC
(125 MHz, CDCl3) 21.2, 25.9, 30.2, 51.5, 75.7, 114.3,
115.1, 124.8, 129.4, 129.6, 130.9, 138.8, 139.0, 146.4,
151.0, 212.0, 284.7; m/z (ESI) 706 MHþ; HRMS (ESI):
4.3.3. (E)-11-(Phenylsulfonyl)-10-undecen-1-ol (4c).
Colourless oil (81%). [Found: C, 65.35; H, 8.20; S, 10.27.
C17H22NO3S) requires C, 65.77; H, 8.44; S, 10.33%]; n
(film) 3370, 2928, 2855, 1447, 1318, 1306, 1289, 1147,
1086, 753, 688, 595 cm21; dH (500 MHz, CDCl3) 1.24–
1.35, 1.41–1.49, 1.51–1.58 (15H, 3m, CH2), 2.23 (2H, m,
CH2), 3.62 (2H, t, J¼6.6 Hz, CH2O), 6.32 (1H, dt, J¼15.1,
1.5 Hz, CHvCHSO2Ph), 6.98 (1H, dt, J¼15.1, 6.9 Hz,
CHvCHSO2Ph), 7.51–7.92 (5H, m, C6H5); dC (125 MHz,
CDCl3) 25.57; 27.43, 28.83, 29.02, 29.17, 29.23, 31.34,
32.60, 62.76, 127.40, 129.12, 130.23, 133.11, 140.67,
147.22; m/z (ESI) 333 ([MþNa]þ); HRMS (ESI) [MþNa]þ,
found 333.1515. C17H26O3SNa requires 333.1495.
4.3.4. Trimethyl-[(E)-3-(phenylsulfonyl)-2-propenyl]-
silane (4d). Colourless oil (33%); n (film) 2956, 2898,
1614, 1447, 1318, 1306, 1291, 1251, 1147, 1086, 856, 754,
689, 596 cm21; dH (500 MHz, CDCl3) 0.02 (9H, s,
(CH3)3Si), 1.76 (2H, dd, J¼1.5, 9.0 Hz, CH2Si), 6.13 (1H,
dt, J¼14.9, 1.2 Hz, CHvCHSO2Ph), 7.03 (1H, dt, J¼14.9,
9.0 Hz, CHvCHSO2Ph), 7.49–7.88 (5H, m, C6H5); dC
(125 MHz, CDCl3) 21.87, 24.36, 127.26, 127.62, 129.10,
132.85, 141.69, 146.43; m/z (EI) 256 (2, Mþ), 237 (10),
199 (3), 147 (45), 125 (11), 115 (23), 91 (8), 77 (100), 59
(11), 51 (8); m/z (ESI) 277 ([MþNa]þ); HRMS (ESI)
[MþNa]þ, found 277.0696. C12H18O2SSiNa requires
277.0689.
MHþ, found 706.0437. C31H Br35Cl2N2O102Ru requires
81
37
706.0489.
4.3. General procedure for cross-metathesis of a,b-
unsaturated sulfones
To a mixture of 2 (0.25 mmol) and vinyl sulfone 3
(0.50 mmol) in CH2Cl2 (15 mL) was added a solution of
catalyst 1 (2.5–10 mol%) in CH2Cl2 (5 mL). The resulting
mixture was stirred at 458C for 2–16 h. The solvent was
removed under reduced pressure. The crude product 4 was
purified by flash chromatography with c-hexane/EtOAc
mixtures.
4.3.5. Diethyl 2-[(E)-3-(phenylsulfonyl)-2-propenyl]-
malonate (4f). Colourless oil (74%); n (film) 2984, 2938,
1731, 1447, 1321, 1308, 1148, 1087, 821, 596 cm21; dH
(200 MHz, CDCl3) 1.23 (6H, t, J¼7.1 Hz, CH3CH2), 2.80
(2H, td, J¼7.4, 1.2 Hz, H2CHvCH), 3.48 (1H, t, J¼7.4 Hz,
CH(CO2Et)2), 4.21 (4H, q, J¼7.1 Hz, CH3CH2), 6.15 (1H,
dt, J¼15.8, 7.0 Hz, CHvCHSO2Ph), 6.48 (1H, dt, J¼15.8,
1.2 Hz, CHvCHSO2Ph), 7.14–7.78 (5H, m, C6H5); dC
(50 MHz, CDCl3) 14.11, 32.22, 52.03, 61.46, 76.65, 77.34,
77.46, 125.61, 126.18, 127.37, 128.50, 132.80, 137.06,
168.90; m/z (EI) 276 (23), 202 (36), 157 (16), 130 (16), 129
(100), 128 (31), 117 (34), 115 (20), 91 (11); HRMS
(LSIMS) MHþ, found 341.1040. C16H21O6S requires
341.1059.
4.3.1. tert-Butyl(dimethyl){[(E)-6-(phenylsulfonyl)-5-
hexenyl]oxy}silane (4a). Colourless oil (90%). n (film)
2952, 2931, 2858, 1321, 1148, 1088, 836, 777, 753, 688,
596, 553 cm21; dH (200 MHz, CDCl3) 0.03 (6H, s,
Si(CH3)2), 0.88 (9H, s, C(CH3)3), 1.46–1.60 (4H, m,
CH 2), 2.20–2.35 (2H, m, CH2), 3.53–3.62 (2H, m,
CH2O), 6.32 (1H, dt, J¼15.1, 1.5 Hz, CHvCHSO2Ph),
7.00 (1H, dt, J¼15.1, 6.8 Hz, CHvCHSO2Ph), 7.47–7.93
(5H, m, C6H5); dC (50 MHz, CDCl3) 25.37, 18.26, 24.04,
25.90, 31.22, 32.00, 62.50, 127.50, 127.65, 129.18, 130.43,
133.16, 140.72, 147.00; m/z (EI) 299 (16), 298 (22), 297
(100), 199 (10), 135 (50), 125 (5), 81 (5), 79 (5), 77 (4), 75
(13), 73 (8); HRMS (LSIMS): MHþ, found 335.1768.
C18H31O3SSi requires 355.1763.
4.3.6. (E)-1-Phenyl-4-(phenylsulfonyl)-3-buten-1-ol (4g).
Colourless oil (71%); n (film) 3487, 3062, 1448, 1307, 1147,
1086, 747, 702, 688, 595, 559 cm21; dH (200 MHz, CDCl3)
2.39–2.73 (2H, m, CH2CHvCH), 4.61–4.92 (1H, m,
CH(OH)Ph), 6.36 (1H, dt, J¼15.1, 1.4 Hz, CHvCHSO2-
Ph), 7.00 (1H, dt, J¼15.1, 7.3 Hz, CHvCHSO2Ph), 7.21–
7.43, 7.46–7.70, 7.77–7.94 (10H, 3m, C6H5); dC (50 MHz,
CDCl3) 40.75, 42.67, 72.63, 73.20, 73.30, 125.60, 125.72,
127.56, 127.76, 127.88, 128.05, 128.38, 128.66, 129.19,
129.32, 129.90, 132.67, 133.25, 133.63, 138.40, 139.50,
140.38, 142.83, 143.80, 143.86; m/z (EI) 182 (13), 168 (19),
144 (26), 129 (27), 125 (100), 107 (23), 97 (11), 79 (17), 78
(11), 77 (67), 51 (26); HRMS (LSIMS) [MþNa]þ, found
311.0715. C16H16O3SNa requires 311.0718.
4.3.2. (E)-6-(Phenylsulfonyl)-5-hexen-1-ol (4b). Colour-
less oil (81%). n (film) 3377, 2935, 2863, 1447, 1306, 1145,
1086, 754, 688, 595, 553 cm21; dH (200 MHz, CDCl3)
1.35–1.63 (4H, m, CH2), 2.21–2.36 (2H, m, CH2), 3.64
(2H, t, J¼6.3 Hz, CH2O), 6.34 (1H, dt, J¼15.1, 1.7 Hz,
CHvCHSO2Ph), 7.00 (1H, dt, J¼15.1, 6.8 Hz,
CHvCHSO2Ph), 7.48–7.92 (5H, m, C6H5); dC (50 MHz,
CDCl3) 23.90, 25.60, 31.18, 31.90, 32.16, 32.20, 62.26,

4530
A. Michrowska et al. / Tetrahedron 59 (2003) 4525–4531
4.3.7. tert-Butyl(dimethyl){(E)-1-phenyl-4-(phenylsul-
fonyl)-3-butenyl]oxy}silane (4h). Colourless oil (55%); n
(film) 2955, 2930, 2857, 1320, 1258, 1147, 1087, 836,
778, 595 cm21; dH (200 MHz, CDCl3) 0.16 (6H, s,
(CH3)2Si), 1.00 (9H, s, C(CH3)3), 2.68–2.80 (2H, m,
CH2CHvCH), 4.97 (1H, t, J¼5.5 Hz, CH(OTBS)Ph),
6.44 (1H, dt, J¼15.1, 1.3 Hz, HvCHSO2Ph), 7.10 (1H,
dt, J¼15.1, 7.4 Hz, CHvCHSO2Ph), 7.32–7.83, 7.94–
8.03 (10H, 2m, C6H5); dC (50 MHz, CDCl3) 25.06,
24.74, 18.08, 25.73, 42.70, 73.37, 125.58, 127.48,
127.65, 128.29, 132.58, 133.17, 140.60, 143.20, 143.61;
m/z (EI) 345 (57), 239 (65), 221 (100), 199 (37), 149
(85), 135 (41), 125 (25), 82 (34), 73 (54), 55 (26), 41
(20); HRMS (LSIMS) [MþNa]þ, found 425.1597. C22-
H30O3SiSNa requires 425.1583.
(EI) 189 (1, MHþ), 145 (4), 133 (6), 119 (33), 96 (18), 93
(14), 81 (70), 75 (13), 67 (54), 55 (100); HRMS (LSIMS)
[MþNa]þ, found 211.0774. C9H16O2NaS requires
211.0763.
4.3.11. (E)-3-Phenyl-1-propenyl vinyl sulfone (4l).
Colourless oil (84%); n (film) 3057, 2921, 1630, 1496,
1384, 1315, 1127, 976, 792 cm21; dH (400 MHz, CDCl3)
3.59 (2H, dd, J¼6.4, 1.7 Hz, PhCH2), 6.05 (1H, d,
J¼9.9 Hz, CHvCH), 6.16 (1H, dt, J¼15.1, 1.7 Hz,
CHvCH), 6.37 (1H, d, J¼16.5 Hz, CHvCH), 6.56 (1H,
dd, J¼16.5, 9.9 Hz, CHvCH), 7.11 (1H, dt, J¼15.1,
6.4 Hz, CHvCH), 7.14–7.18, 7.24–7.37 (5H, 2m, C6H5);
dC (100 MHz, CDCl3) 37.74, 127.13, 128.72, 128.84,
128.83, 128.89, 129.73, 136.01, 137.44, 147.66; m/z (EI)
208 (11, Mþ), 163 (3), 142 (5), 128 (2), 117 (100), 103 (2),
91 (34), 89 (7), 77 (6), 65 (13); HRMS (EI) Mþ, found
208.0556. C11H12O2S requires 208.0558.
4.3.8. (E)-5-Methoxy-1-(methoxymethyl)-3[(4-methyl-
phenyl)sulfonyl]-H-indol-4-yl-1-propenyl phenyl sulfone
(4i). Colourless crystals, mp 140–1418C (54%). [Found: C,
61.46; H, 5.35; N, 2.76. C17H27NO6S2 requires C, 61.70; H,
5.18; N, 2.66%]; n (KBr) 3532, 3119, 2926, 2852, 1627,
1514, 1286, 1143, 1085, 1027, 798, 676, 593 cm21; dH
(500 MHz, CDCl3) 2.43 (3H, s, C6H4CH3), 3.32 (3H, s,
CH3O), 3.58 (3H, s, CH3O), 3.96 (2H, dd, J¼5.8, 1.5 Hz,
CH2CHvCH), 5.46 (2H, s, CH2OMe), 5.74 (1H, dt,
J¼15.0, 1.5 Hz, CHvCHSO2Ph), 6.54 (1H, dt, J¼15.0,
5.8 Hz, CHvCHSO2Ph), 6.92 (1H, d, J¼9 Hz, ArH), 7.25–
7.32 (2H, m0, ArH), 7.39–7.56 (4H, m, ArH), 7.66–7.77
(4H, AA0XX , C6H4CH3), 8.08 (1H, s, ArH); dC (125 MHz,
CDCl3) 21.64, 29.67, 56.24, 56.40, 78.59, 109.58, 110.64,
115.42, 116.63, 124.42, 126.54, 127.20, 128.90, 129.13,
130.06, 132.75, 137.44, 139.50, 141.30, 144.35, 145.76,
154.20; m/z (EI) 525 (5, Mþ), 494 (6), 384 (52), 370 (37),
366 (10), 349 (12), 306 (16), 229 (47), 214 (20), 198 (31),
184 (16), 169 (17), 105 (38), 77 (19).
4.3.12. tert-Butyl-dimethyl-[7-(toluene-4-sulfonyl)-hept-
5-enyloxy]-silane (10a). Colourless oil (99%; (E)/(Z)
84:16). [Found: C, 62.61; H, 8.86; S, 8.26. C20H34O3SSi
requires C, 62.78; H, 8.79; S, 8.14%]; n (film) 2930, 2858,
1598, 1472, 1320, 1302, 1255, 1143, 1089, 836, 776 cm21
;
dH (500 MHz, CDCl3) 0.04 (6H, s, Si(CH3)3), 0.88 (9H, s,
C(CH3)3), 1.29–1.37 (2H, m, CH2), 1.39–1.46 (2H, m,
CH2), 2.02 (2H, m, CH2CHv), 2.44 (3H, s, CH3), 3.56 (2H,
t, J¼6.3 Hz, CH2OTBS), 3.72 (2H, d, J¼7.2 Hz, CH2SO2),
5.36–5.44 (1H, m, CHvCH), 5.47–5.55 (1H, m,
CHvCH), 7.31–7.35 (2H, m, ArH), 7.71–7.76 (2H, m,
ArH) (isomer (E)); dC (125 MHz, CDCl3) 25.33, 18.30,
21.56, 24.95, 25.92, 27.01, 32.23, 60.18, 62.77, 116.25,
128.52, 129.58, 135.55, 141.34, 144.44 (isomer (E)); m/z
(EI) 325 (11), 231 (30), 227 (6), 215 (9), 213 (100), 155 (5),
149 (77), 139 (11), 95 (25), 91 (11), 73 (6); HRMS (LSIMS)
MHþ, found 383.1059. C20H35O3SSi requires 383.2078.
4.3.9. (E)-1-Nonadecenyl vinyl sulfone (4j). Colourless
waxy solid (59%). [Found: C, 70.55; H, 11.21; S, 8.78.
C21H40O2NS requires C, 70.73; H, 11.31; S, 8.99%]; n
4.3.13. Di[(E)-1-heptenyl] sulfone (6k). To a mixture of
1-heptene 2k (353 mg, 3.6 mmol, 4 equiv.) and divinyl
sulfone 3b (106 mg, 0.9 mmol, 1 equiv.) in CH2Cl2 (25 mL)
was added a solution of catalyst 1c (38 mg, 5 mol%) in
CH2Cl2 (5 mL). The resulting mixture was stirred at 458C
for 16 h. The solvent was removed under reduced pressure
and the residue was purified by flash chromatography (5%
EtOAc/c-hexane) to give the monosubstituted product 4k
(106 mg, 60%) and the title compound 6k (35 mg, 14%) as a
colourless oils. 6k: n (film) 3047, 2957, 2931, 2860, 1634,
1467, 1319, 1293, 1131, 984, 830, 608 cm21; dH (500 MHz,
CDCl3) 0.90 (6H, t, J¼6.8 Hz, CH3), 1.26–1.37 (8H, m,
CH2), 1.42–1.51 (4H, m, CH2), 2.20–2.28 (4H, m, CH2),
6.21 (2H, dt, J¼15.1, 1.5 Hz, CHvCHSO2), 6.88 (1H, dt,
J¼15.1, 6.8 Hz, CHvCHSO2); dC (125 MHz, CDCl3)
13.87, 22.33, 27.29, 31.18, 31.51, 129.53, 147.79; m/z
(ESI) 259 (1, MHþ), 215 (9), 203 (14), 187 (2), 163 (35), 95
(40), 91 (15), 81 (51), 67 (41); HRMS (ESI) [MþNa]þ,
found 281.1551. C14H26O2NaS requires 281.1546.
(film) 2918, 2849, 1629, 1472, 1305, 1125, 967, 730 cm21
;
dH (400 MHz, CDCl3) 0.87 (3H, t, J¼6.9 Hz, CH3), 1.18–
1.36 (28H, m, CH2), 1.46 (2H, q, J¼7.3 Hz, CH2), 2.26 (2H,
tdd, J¼7.0, 6.8, 1.5 Hz, CH2), 6.04 (1H, d, J¼9.8 Hz,
CHvCH), 6.22 (1H, dt, J¼15.2, 1.5 Hz, CHvCH), 6.38
(1H, d, J¼16.6 Hz, CHvCH), 6.58 (1H, dd, J¼16.6,
9.8 Hz, CHvCH), 6.94 (1H, dt, J¼15.2, 6.8 Hz, CHvCH);
dC (100 MHz, CDCl3) 14.10, 22.67, 27.53, 29.02, 29.27,
29.34, 29.44, 29.57, 29.61, 29.64, 29.67, 31.66, 31.90,
128.29, 128.47, 137.75, 149.58; m/z (EI) 357 (1, Mþ), 339
(14), 321 (5), 313 (1), 290 (3), 264 (2), 123 (30), 109 (55),
95 (85), 81 (100); HRMS (LSIMS) [MþNa]þ, found
379.2650. C21H40O2NaS requires 379.2641.
4.3.10. (E)-1-Heptenyl vinyl sulfone (4k). Colourless oil
(42%); n (film) 3055, 2961, 2859, 1627, 1462, 1316, 1261,
1129, 1016, 818, 799 cm21; dH (400 MHz, CDCl3) 0.90
(3H, t, J¼7.0 Hz, CH3), 1.26–1.37 (4H, m, CH2), 1.48 (2H,
q, J¼7.4 Hz, CH2), 2.27 (2H, tdd, J¼6.9, 6.8, 1.6 Hz, CH2),
6.06 (1H, d, J¼9.8 Hz, CHvCH), 6.23 (1H, dt, J¼15.1,
1.6 Hz, CHvCH), 6.39 (1H, d, J¼16.6 Hz, CHvCH), 6.58
(1H, dd, J¼9.8, 16.6 Hz, CHvCH), 6.95 (1H, dt, J¼15.1,
6.8 Hz, CHvCH); dC (100 MHz, CDCl3) 13.86, 22.30,
27.19, 31.14, 31.60, 128.29, 128.48, 137.72, 149.60; m/z
4.4. Homo cross-metathesis of 2a
4.4.1. 1,10-Bis-(tert-butyl-dimethylsilanyloxy)-dec-5-ene
(5a). To a mixture of 2a (171 mg, 0.8 mmol) in CH2Cl2
(2 mL) a solution of catalyst 1a (30 mg, 5 mol%) in CH2Cl2
(2 mL) was added. The resulting mixture was stirred at 458C

A. Michrowska et al. / Tetrahedron 59 (2003) 4525–4531
4531
7. (a) Huang, J.; Stevens, E. D.; Nolan, S. P. J. Am. Chem. Soc.
1999, 121, 2674–2678. (b) Scholl, M.; Trnka, T. M.; Morgan,
J. P.; Grubbs, R. H. Tetrahedron Lett. 1999, 40, 2247–2250.
(c) Ackermann, L.; Fu¨rstner, A.; Weskamp, T.; Kohl, F. J.;
Herrmann, W. A. Tetrahedron Lett. 1999, 40, 4787–4790.
8. For example: (a) Paquette, L. A.; Leit, S. M. J. Am. Chem. Soc.
1999, 121, 8926–8927. (b) Paquette, L. A.; Fabris, F.; Tae, J.;
Gallucci, J. C.; Hofferberth, J. E. J. Am. Chem. Soc. 2000, 122,
3391–3398. (c) Fu¨rstner, A.; Gastner, T.; Weintritt, H. J. Org.
Chem. 1999, 64, 2361–2366. (d) Fu¨rstner, A.; Ackermann, L.
Chem. Commun. 1999, 95–98.
for 16 h. The solvent was removed under reduced pressure
and the product was purified by flash chromatography
(c-hexane) to give the title compound 5a (148 mg, 92%) as a
colourless oil ((E)/(Z) 85:15). [Found: C, 65.52; H, 11.96.
C22H48O2Si2 requires C, 65.93; H, 12.07%]; n(film) 2930,
2858, 1472, 1388, 1255, 1103, 1006, 836, 774 cm21; dH
(500 MHz, CDCl3) 0.07 (12H, s, Si(CH3)3), 0.92 (18H, s,
C(CH3)3), 1.37–1.45 (4H, m, CH2), 1.50–1.58 (4H, m,
CH2), 1.97–2.05 (4H, m, CH2), 3.60–3.66 (4H, m, CH2-
OTBS), 5.40–5.45 (2H, m, CHvCH) (isomer (E)); dC
(125 MHz, CDCl3) 25.27, 1.01, 18.37, 25.82, 25.99, 32.46,
63.16, 130.35 (isomer (E)); m/z (IE) 343 (2), 234 (2), 233
(8), 219 (1), 189 (12), 147 (60), 137 (10), 95 (100), 89 (11),
81 (99), 75 (65), 69 (18), 67 (44), 59 (12); HRMS (ESI)
[MþNa]þ, found 423.3107. C22H48O2NaSi2 requires
423.3085.
9. (a) Chatterjee, A. K.; Grubbs, R. H. Org. Lett. 1999, 1,
1751–1753. (b) Blackwell, H. E.; O’Leary, D. J.; Chatterjee,
A. K.; Washenfelder, R. A.; Bussmann, D. A.; Grubbs, R. H.
J. Am. Chem. Soc. 2000, 122, 58–71.
10. Yao, Q. Org. Lett. 2002, 4, 427–430.
11. (a) Hanson, P. R.; Probst, D. A.; Robinson, R. E.; Yau, M.
Tetrahedron Lett. 1999, 40, 4761–4764. (b) Wanner, J.;
Harned, A. M.; Probst, D. A.; Poon, K. W. C.; Klein, T. A.;
Snelgrove, K. A.; Hanson, P. R. Tetrahedron Lett. 2002, 43,
917–921.
Acknowledgements
This work was supported by the State Committee of
Scientific Research (Grant No. 4 T09A 136 22). K. G.
wishes to thank the Alexander von Humboldt foundation for
books and equipment donation.
12. Karsch, S.; Metz, P. Synlett 2002, 2019–2022.
13. (a) Basu, K.; Cabral, J. A.; Paquette, L. A. Tetrahedron Lett.
2002, 43, 5453–5456. (b) Randl, S.; Connon, S. J.; Blechert,
S. Chem. Commun. 2001, 1796–1797.
14. Crowe, W. E.; Goldberg, D. R. J. Am. Chem. Soc. 1995, 117,
5162–5163.
References
15. It should be noted, however, that the structurally very similar
complex 1d was found to be not reactive in cross-metathesis of
vinyl sulfones: Chatterjee, A. K.; Morgan, J. P.; Scholl, M.;
Grubbs, R. H. J. Am. Chem. Soc. 2000, 122, 3783–3784.
16. Grela, K.; Harutyunyan, S.; Michrowska, A. Angew. Chem.
Int. Ed. Engl. 2002, 41, 4038–4040.
1. For reviews, see: (a) Procter, D. J. J. Chem. Soc. Perkin Trans.
1 1999, 641–667. (b) Simpkins, N. S. Tetrahedron 1990, 46,
6951–6984. (c) In The Chemistry of Sulphones and
Sulphoxides; Patai, S., Rappaport, Z., Stirling, C., Eds.;
Wiley: New York, 1988. For representative recent appli-
17. (a) Randl, S.; Gessler, S.; Wakamatsu, H.; Blechert, S. Synlett
2001, 430–432. (b) Imhof, S.; Randl, S.; Blechert, S. Chem.
Commun. 2001, 1692–1693. (c) Grela, K.; Kim, K. M. Eur.
J. Org. Chem. 2003, 963–966.
´
cations, see e.g.: (d) Mauleon, P.; Alonso, I.; Carretero, J. C.
Angew. Chem. Int. Ed. 2001, 40, 1291–1293. (e) Bentley,
P. A.; Bickley, J. F.; Roberts, S. M.; Steiner, A. Tetrahedron
Lett. 2001, 42, 3741–3743. (f) Lusinchi, M.; Stanbury, T. V.;
Zard, S. Z. Chem. Commun. 2002, 1532–1533. (g) Fahrat, S.;
Marek, I. Angew. Chem. Int. Ed. 2002, 41, 1410–1412.
(h) Teyssot, M. L.; Fayolle, M.; Philouze, C.; Dupuy, C. Eur.
J. Org. Chem. 2002, 54–62.
18. Liras, S.; Davoren, J. E.; Bordner, J. Org. Lett. 2001, 3,
703–706.
19. For the metathesis of enantiopure h 4-(1-sulfinyldiene)-iron(0)
tricarbonyl complexes (protected vinyl sulfoxides), see: Paley,
R. S.; Estroff, L. A.; Gauguet, J.-M.; Hunt, D. K.; Newlin, R. C.
Org. Lett. 2000, 2, 365–368.
2. Grela, K.; Bieniek, M. Tetrahedron Lett. 2001, 42,
6425–6428.
20. (a) Ahn, Y. M.; Yang, K.; Georg, G. I. Org. Lett. 2001, 3,
1411–1413. For recent application, see: Stymiest, J. L.;
Mitchell, B. F.; Wong, S.; Vederas, J. C. Org. Lett. 2003, 5,
47–49.
3. (a) Morgan, J. P.; Grubbs, R. H. Org. Lett. 2000, 2,
3153–3155. (b) Scholl, M.; Ding, S.; Lee, C. W.; Grubbs,
R. H. Org. Lett. 1999, 1, 953–956. (c) Bielawski, C. W.;
Grubbs, R. H. Angew. Chem. Int. Ed. 2000, 39, 2903–2906.
4. (a) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H.
Angew. Chem. Int. Ed. Engl. 1995, 34, 2039–2041. (b) Wu, Z.;
Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc.
1995, 117, 5503–5511. (c) Schwab, P.; Grubbs, R. H.; Ziller,
J. W. J. Am. Chem. Soc. 1996, 118, 100–110.
21. A referee suggested that the inability of vinyl sulfoxides to
participate in the CM reaction can be also explained by a
red-ox catalyst degradation, as it is known that sulfoxides can
oxidise Fisher-type carbenes, cf: Wienand, A.; Reissig, H. U.
Organometallics 1990, 9, 3133–3142, We gratefully acknowl-
edge a referee for pointing out this possibility.
5. (a) Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.;
DiMare, M.; O’Regan, M. J. Am. Chem. Soc. 1990, 112,
3875–3886. (b) Bazan, G. C.; Oskam, J. H.; Cho, H.-N.; Park,
L. Y.; Schrock, R. R. J. Am. Chem. Soc. 1991, 113,
6899–6907.
22. (a) Makosza, M.; Nieczypor, P.; Grela, K. Tetrahedron 1998,
54, 10827–10836. (b) Makosza, M.; Stalewski, J.;
Wojciechowski, K.; Danikiewicz, W. Tetrahedron 1997, 53,
193–214. (c) Prowotorow, I.; Wicha, J.; Mikami, K. Synthesis
2001, 145–149. (d) Sas, W. Chem. Commun. 1984, 862–863.
(e) Weichert, A.; Hoffmann, H. M. R. J. Org. Chem. 1991, 56,
4098–4112.
6. (a) Shon, Y.-S. S.; Lee, T. R. Tetrahedron Lett. 1997, 38,
1283–1286. (b) Spagnol, G.; Heck, M.-P.; Nolan, S. P.;
Mioskowski, C. Org. Lett. 2002, 4, 1767–1770.